CN112675850A - Nickel catalyst, preparation method thereof and synthesis method of pyrimidine derivatives - Google Patents
Nickel catalyst, preparation method thereof and synthesis method of pyrimidine derivatives Download PDFInfo
- Publication number
- CN112675850A CN112675850A CN202011541701.8A CN202011541701A CN112675850A CN 112675850 A CN112675850 A CN 112675850A CN 202011541701 A CN202011541701 A CN 202011541701A CN 112675850 A CN112675850 A CN 112675850A
- Authority
- CN
- China
- Prior art keywords
- nickel
- catalyst
- nickel catalyst
- pyrimidine
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 150000003230 pyrimidines Chemical class 0.000 title claims abstract description 41
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 title claims abstract description 22
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 25
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004480 active ingredient Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 239000005909 Kieselgur Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- -1 amidoxime amine Chemical class 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 150000003222 pyridines Chemical class 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- QTVOTIBHDWOQJP-UHFFFAOYSA-N 2-(3,4-difluorophenyl)-5-propylpyrimidine Chemical compound N1=CC(CCC)=CN=C1C1=CC=C(F)C(F)=C1 QTVOTIBHDWOQJP-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- RTTWLTLNKLTUJR-UHFFFAOYSA-N 2-methylidenepentanal Chemical compound CCCC(=C)C=O RTTWLTLNKLTUJR-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000006146 oximation reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- BGEYOSFUJVDPRV-UHFFFAOYSA-N 2-(4-ethylphenyl)-5-propylpyrimidine Chemical compound N1=CC(CCC)=CN=C1C1=CC=C(CC)C=C1 BGEYOSFUJVDPRV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- SXFFMFAQNAFSLF-UHFFFAOYSA-N 4-ethylbenzonitrile Chemical compound CCC1=CC=C(C#N)C=C1 SXFFMFAQNAFSLF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BTBFCBQZFMQBNT-UHFFFAOYSA-N 3,4-difluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1F BTBFCBQZFMQBNT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- NMVVJCLUYUWBSZ-UHFFFAOYSA-N aminomethylideneazanium;chloride Chemical compound Cl.NC=N NMVVJCLUYUWBSZ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- DNMZJIGSDQVGSA-UHFFFAOYSA-N methoxymethane;hydrochloride Chemical compound Cl.COC DNMZJIGSDQVGSA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- MYXKPFMQWULLOH-UHFFFAOYSA-M tetramethylazanium;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].C[N+](C)(C)C MYXKPFMQWULLOH-UHFFFAOYSA-M 0.000 description 1
Images
Abstract
The invention provides a nickel catalyst, a preparation method thereof and a synthesis method of pyrimidine derivatives. The nickel catalyst comprises an active component and a carrier, wherein the active component comprises nickel oxide, and the specific surface area of the carrier is 2300-2800 m2(ii) in terms of/g. The nickel catalyst having the above composition has a large specific surface area, and the active ingredient is nickel oxide. The application of the pyridine derivative in the cyclization reaction taking 2-alkylacrolein and amidoxime as raw materials can greatly improve the selectivity and catalytic efficiency of the reaction, thereby being beneficial to greatly improving the yield and purity of the pyrimidine derivative.
Description
Technical Field
The invention relates to the field of synthesis of pyrimidine derivatives, and particularly relates to a nickel catalyst, a preparation method of the nickel catalyst and a synthesis method of the pyrimidine derivatives.
Background
The pyrimidine-based liquid crystal is a compound containing one or more pyrimidine rings in a liquid crystal molecule. The nitrogen heterocyclic ring liquid crystal is an important liquid crystal material and is widely applied to modern liquid crystal display, in particular to a multiplex-driven high-grade TN-LCD. The liquid crystal material is characterized by low viscosity, good orientation in electric field, low polarity, high voltage holding ratio and high resistivity. Therefore, the compound is not only an important component of the super-twisted nematic liquid crystal display material, but also widely applied to the formula of the ferroelectric liquid crystal material.
The most commonly used synthetic method for preparing pyrimidine derivatives is to prepare methyl imido methyl ether hydrochloride by nitrile, methanol and dry hydrogen chloride gas, then prepare formamidine hydrochloride with ethanol solution of ammonia, and then perform cyclization with 2-alkyl-3-dimethylamino acrolein to obtain a target product as shown in reaction 1-1:
the method has the defects that the yield of the pyrimidine derivatives is low (only about 50 percent), the three wastes pollute the environment greatly, the requirement on equipment is high, the steps are complicated, the production cost is high, and the method is not beneficial to industrial production.
Disclosure of Invention
The invention mainly aims to provide a nickel catalyst, a preparation method thereof and a synthesis method of a pyrimidine derivative, and aims to solve the problems of low yield, poor environmental protection, complex process flow and high cost in the preparation of the pyrimidine derivative by the existing method.
In order to achieve the above object, one aspect of the present invention provides a nickel catalyst comprising an active ingredient and a carrier, wherein the active ingredient comprises nickel oxide, and the carrier has a specific surface area of 2300 to 2800m2/g。
Furthermore, in the nickel catalyst, the loading amount of nickel oxide is 6-8 wt%.
Further, the support is selected from one or more of the group consisting of activated carbon, diatomaceous earth and alumina.
In another aspect, the present application further provides a method for preparing the nickel catalyst provided herein, the method comprising: in the presence of a carrier, carrying out a precipitation reaction on soluble nickel salt and an alkaline aqueous solution so as to load a product of the precipitation reaction in the carrier to obtain a precursor; and roasting the precursor to obtain the nickel catalyst.
Further, the temperature of the roasting step is 380-430 ℃.
Further, the soluble nickel salt is selected from one or more of the group consisting of nickel chloride, nickel bromide and nickel sulfate; the alkali in the alkaline aqueous solution is selected from one or more of the group consisting of sodium carbonate, potassium carbonate and lithium carbonate; preferably, the ratio of moles of soluble nickel salt to moles of base in the aqueous alkaline solution is 1: (1.1-1.5).
In another aspect of the present application, a method for synthesizing a pyrimidine derivative is provided, the method comprising: in the presence of the nickel-containing catalyst, a first alkaline reagent, an inert atmosphere and a first organic solvent, 2-alkylacrolein and amidoxime amine are subjected to a cyclization reaction to obtain the pyrimidine derivative, wherein the synthetic route is as follows:
wherein R is1Is selected from C1~C15Fat of (C)1~C30Aryl and C1~C30Cycloalkyl, or a substituent formed by substitution of the above groups by oxygen atoms, halogen or nitrogen atoms, R2Is C1~C15The first organic solvent comprises a first component and a second component, the first component is an alcohol solvent, and the second component is one or more of cyclohexane, petroleum ether, n-hexane and n-heptane.
Further, the molar ratio of the amidoxime, the 2-alkyl acrolein, the nickel-containing catalyst and the first alkaline agent is 1 (1.05-1.5) to (0.01-0.05) to (1.0-1.5).
Further, the temperature of the ring closing reaction is 40-90 ℃.
Further, the first alkaline agent is selected from one or more of the group consisting of sodium methoxide, sodium carbonate, potassium carbonate, sodium hydroxide and tetramethylammonium hydroxide.
By applying the technical scheme of the invention, the nickel catalyst with the composition has a large specific surface area, and the active component is nickel oxide. The application of the pyridine derivative in the cyclization reaction taking 2-alkylacrolein and amidoxime as raw materials can greatly improve the selectivity and catalytic efficiency of the reaction, thereby being beneficial to greatly improving the yield and purity of the pyrimidine derivative.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a gas phase diagram of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine obtained in example 2-1 of the present invention;
FIG. 2 shows a mass spectrum of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine obtained in example 2-1 of the present invention;
FIG. 3 shows a gas phase diagram of 2- (4-ethyl-phenyl) -5-propyl-pyrimidine obtained in example 2-2 of the present invention;
FIG. 4 shows a mass spectrum of 2- (4-ethyl-phenyl) -5-propyl-pyrimidine obtained in example 2-2 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the problems of low yield, poor environmental protection, complex process flow and high cost exist when the existing method is adopted to prepare the pyrimidine derivatives. In order to solve the technical problem, the application provides a nickel catalyst which comprises an active component and a carrier, wherein the active component comprises nickel oxide, and the specific surface area of the carrier is 2300-2800 m2/g。
The nickel catalyst having the above composition has a large specific surface area, and the active ingredient is nickel oxide. The application of the pyridine derivative in the cyclization reaction taking 2-alkylacrolein and amidoxime as raw materials can greatly improve the selectivity and catalytic efficiency of the reaction, thereby being beneficial to greatly improving the yield and purity of the pyrimidine derivative.
In order to further improve the yield and purity of the pyrimidine derivative, the loading amount of nickel oxide can be adjusted, and preferably, the loading amount of nickel oxide in the nickel catalyst is 6-8%.
The carrier used in the above nickel catalyst may be selected from carriers commonly used in the art, and preferably, the above carriers include, but are not limited to, one or more of the group consisting of activated carbon, diatomaceous earth and alumina.
Another aspect of the present application also provides a method for preparing the nickel catalyst provided by the present application, the method comprising: in the presence of a carrier, carrying out a precipitation reaction on soluble nickel salt and an alkaline aqueous solution so as to load a product of the precipitation reaction in the carrier to obtain a precursor; and roasting the precursor to obtain the nickel catalyst.
In the above-mentioned production method, during the precipitation reaction, nickel ions react with an alkaline substance in the alkaline aqueous solution to form a precipitate (the composition of the precipitate varies depending on the kind of the alkaline agent). The precipitate is adsorbed in the carrier due to the high specific surface area of the carrier. The precipitate is then decomposed during calcination to form nickel oxide.
In a preferred embodiment, the temperature of the calcination step is 380 to 430 ℃. When the calcination temperature is low, the decomposition of the precipitated product is less complete, resulting in a low content of nickel oxide in the nickel catalyst. The application process needs to increase the dosage of the nickel catalyst to improve the activity and selectivity of the reaction. When the roasting temperature is too high, energy waste is caused, and the process cost is increased.
In the above preparation method, the soluble nickel salt and the alkaline substance in the alkaline aqueous solution may be selected from those commonly used in the art. For example, soluble nickel salts include, but are not limited to, one or more of the group consisting of nickel chloride, nickel bromide, and nickel sulfate; the base in the basic aqueous solution includes, but is not limited to, one or more of the group consisting of sodium carbonate, potassium carbonate, and lithium carbonate.
Since the soluble nickel salt is expensive, in order to further increase the utilization rate of the soluble nickel salt and the production rate of nickel oxide, it is preferable that the molar ratio of the soluble nickel salt to the alkali in the aqueous alkaline solution is 1: (1.1-1.5).
In another aspect of the present application, a method for synthesizing a pyrimidine derivative is provided, where the method for synthesizing the pyrimidine derivative includes: in the presence of the nickel-containing catalyst, a first alkaline reagent, an inert atmosphere and a first organic solvent, 2-alkylacrolein and amidoxime amine are subjected to a cyclization reaction to obtain a pyrimidine derivative, wherein the synthetic route is as follows:
wherein R is1Is C1~C15Fat of (C)1~C30Aryl and C1~C30Cycloalkyl, or a substituent formed by substitution of the above groups by oxygen atoms, halogen or nitrogen atoms, R2Is C1~C15The first solvent comprises a first component and a second component, the first component is an alcohol solvent, and the second component is one or more of cyclohexane, petroleum ether, n-hexane and n-heptane.
In the synthesis method of the pyrimidine derivatives, the addition of the nickel catalyst is beneficial to greatly improving the selectivity and the reaction rate of the cyclization reaction, thereby being beneficial to greatly improving the yield and the purity of the pyrimidine derivatives. Meanwhile, in the cyclization reaction process, 2-alkylacrolein is easy to dissolve in a cyclohexane solvent (a first phase layer), amidoxime and a first alkaline solvent are dissolved in an alcohol solvent (a second phase layer), so that the two reaction raw materials respectively exist in the two phase layers, and the cyclization reaction is carried out at the interface of the two phase layers, so that the 2-alkylacrolein can be inhibited from deteriorating, and the pyrimidine derivative can be obtained by carrying out a simple separation process after the cyclization reaction is finished, so that the utilization rate of the raw materials is improved, and the process flow is simplified. In conclusion, the synthesis method is favorable for greatly improving the utilization rate of raw materials, simplifying the process flow and simultaneously improving the yield and purity of the pyrimidine derivatives and the environmental protection of the process.
In the above-mentioned ring-closing reaction, the amount of each raw material may be added in accordance with the theoretical amount. In a preferred embodiment, the molar ratio of the amidoxime, the 2-alkylacrolein, the nickel-containing catalyst and the first alkaline agent is 1 (1.05-1.5) to (0.01-0.05) to (1.0-1.5). The ratio of the moles of the amidoxime, the 2-alkylacrolein, the nickel-containing catalyst and the first alkaline agent includes, but is not limited to, the above range, and it is advantageous to further improve the yield and purity of the pyrimidine derivative and the environmental protection of the process by limiting the ratio to the above range.
In a preferred embodiment, the temperature of the ring closure reaction is 40 to 90 ℃. When the temperature in the process of the ring closing reaction is lower, the reaction rate of the ring closing reaction is lower, and the reaction time is longer. When the temperature during the ring-closing reaction is high, the 2-alkylacrolein is easy to polymerize, which affects the utilization rate of the 2-alkylacrolein and the yield and purity of the pyrimidine derivatives prepared subsequently.
In the synthesis process of the pyrimidine derivatives, the addition of the first alkaline reagent is beneficial to improving the reactivity of the cyclization reaction. Preferably, the first alkaline agent includes, but is not limited to, one or more of the group consisting of sodium methoxide, sodium carbonate, potassium carbonate, sodium hydroxide, and tetramethylammonium hydroxide.
In a preferred embodiment, the alcoholic solvent includes, but is not limited to, one or more of the group consisting of methanol, ethanol, and propanol. The amounts of the alcohol solvent and the cyclohexane solvent are not particularly limited as long as the corresponding solutes thereof can be dissolved.
In order to further improve the yield and purity of the pyrimidine derivative, preferably, the synthesis method of the pyrimidine derivative further comprises: and after the cyclization reaction is finished, sequentially carrying out liquid separation, water washing, organic layer column adsorption, solvent removal and recrystallization on a product system of the cyclization reaction to obtain the required pyrimidine derivative.
The above-mentioned liquid separation process and water washing step may be repeated several times, but in order to reduce the loss of the pyrimidine derivative, it is preferable to perform the organic layer column adsorption step when the pH of the aqueous phase is 7 to 8.
In the process of synthesizing the pyrimidine derivatives, the adopted amidoxime can be a commercially available product and can be synthesized by itself. In an alternative embodiment, the method for synthesizing the pyrimidine derivative further comprises: a step for preparing a amidoxime, comprising: in the presence of a second basic reagent and a second organic solvent, carrying out oximation reaction on nitrile organic matter corresponding to the amidoxime and hydroxylamine hydrochloride to obtain the amidoxime.
The second basic agent is used to increase the reactivity of the oximation reaction, and preferably, the second basic agent includes, but is not limited to, one or more of the group consisting of triethylamine, sodium carbonate, and sodium hydroxide.
In order to further increase the yield of amidoxime, the molar ratio of the hydroxylamine hydrochloride, the nitrile organic compound corresponding to amidoxime and the second basic reagent is preferably 1: (0.3-0.8): (1.0-1.5).
In order to increase the degree of the oximation reaction, the oximation reaction may be carried out in a second organic solvent. Preferably, the above organic solvent includes, but is not limited to, one or more of the group consisting of ethanol, methanol and isopropanol.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Preparation of nickel catalyst
Examples 1 to 1
The preparation method of the nickel oxide loaded activated carbon is as follows: adding 30g of nickel chloride into a 500ml three-neck bottle, adding 200g of water, stirring, dissolving, and adding 200g of activated carbon (200-250 meshes, and the specific surface area is 1800 m)2Per g), 150g of 20% sodium carbonate are addedStirring the aqueous solution at 55 +/-5 ℃ for reacting for 3 hours, cooling, filtering, washing with deionized water for 2 times, drying, decomposing and activating at the high temperature of 400 ℃ to obtain 210g of the prepared nickel oxide supported activated carbon catalyst, wherein the loading capacity of the nickel oxide is 7.5 percent, which is marked as catalyst A1, and the specific surface area is 2500m2/g。
Examples 1 to 2
The differences from example 1-1 are: the carrier is diatomite.
The nickel oxide-supported diatomaceous earth catalyst, the nickel oxide loading of 6.3%, reported as catalyst A2, had a specific surface area of 110m2/g。
Examples 1 to 3
The differences from example 1-1 are: the carrier is alumina.
The nickel oxide-supported alumina catalyst had a nickel oxide loading of 6.2%, which was designated as catalyst A3 and a specific surface area of 350m2/g。
Examples 1 to 4
The differences from example 1-1 are: the calcination temperature was 390 ℃.
The nickel oxide supported activated carbon catalyst has the nickel oxide supporting amount of 6 percent, which is recorded as catalyst A4, and the specific surface area of the catalyst is 2350m2/g。
Examples 1 to 5
The differences from example 1-1 are: the calcination temperature was 430 ℃.
The nickel oxide supported activated carbon catalyst has a nickel oxide supporting amount of 7.2%, which is recorded as catalyst A5, and the specific surface area of the catalyst is 2780m2/g。
Examples 1 to 6
The differences from example 1-1 are: the calcination temperature was 410 ℃.
The nickel oxide supported activated carbon catalyst, the nickel oxide loading of which was 6.5%, was designated as catalyst A6, the specific surface area of which was 2600m2/g。
Synthesis method of pyrimidine derivatives
Example 2-1
A method for synthesizing pyrimidine derivatives comprises the following steps:
(1) preparation of amidoximes.
Firstly, adding 180ml of ethanol, 41.7g (0.3mol) of 3, 4-difluorobenzonitrile, 62.5g (0.9mol) of hydroxylamine hydrochloride and 97g (0.96mol) of triethylamine into a 500ml glass three-necked bottle, fully replacing with nitrogen, carrying out reflux reaction for 6h, controlling by TLC, ensuring that the raw materials are qualified, stirring under the protection of nitrogen, cooling to 15 +/-5 ℃, pouring into 200ml of water for hydrolysis, carrying out suction filtration on the solid, washing the filter cake with 150ml of water to be neutral, and airing to obtain 49g of crude product (51.6 g theoretically) of 3, 4-difluorohydroxamine, wherein the yield is 94.96 wt%, and the liquid phase purity is 97%.
(2) And (3) synthesizing pyrimidine derivatives.
Into a 1000ml glass three-necked flask, 43g (0.25mol) of 3, 4-difluorohydroxamine, 60ml of methanol, 500ml of cyclohexane, 16.2g (0.3mol) of sodium methoxide and 0.5g of nickel oxide-supported activated carbon (catalyst A1) were charged. Stirring and controlling the temperature to 45 ℃ under the protection of nitrogen, slowly dropping 36.75g (0.375mol) of 2-propyl acrolein, carrying out heat preservation reaction for 8h after dropping, controlling in TLC, ensuring that the raw material is qualified, separating liquid, washing an organic layer to be neutral by 100ml of water, passing 10g of silica gel and 5g of alumina through a column, carrying out reduced pressure concentration on a filtrate to obtain 58.3g of a crude product of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine, crystallizing the crude product for three times by using 100ml of ethanol to be qualified, airing, 52.65g (58.5 g of theory), ensuring the yield to be 90 wt% and detecting the purity by a gas phase (99.9%). The gas phase spectrum is shown in figure 1, and the mass spectrum is shown in figure 2.
Examples 2 to 2
(1) Preparation of amidoximes.
The raw materials and the target product are shown in the following reaction equation: firstly, adding 180ml of ethanol, 39.3g (0.3mol) of 4-ethyl benzonitrile, 62.5g (0.9mol) of hydroxylamine hydrochloride and 80.64g (0.96mol) of sodium bicarbonate into a 500ml glass three-necked bottle, fully replacing with nitrogen, carrying out reflux reaction for 6 hours, carrying out TLC (thin layer chromatography) central control, ensuring that the raw materials are qualified, stirring under the protection of nitrogen, cooling to 15 +/-5 ℃, pouring into 200ml of water for hydrolysis, carrying out suction filtration on the solid, washing the filter cake to be neutral by 150ml of water, and airing to obtain 46.2g of crude product (49.2 g theoretically) of 4-ethyl benzoximamine, wherein the yield is 93.9 wt% and the liquid phase purity is 95%.
(2) And (3) synthesizing pyrimidine derivatives.
Into a 1000ml glass three-necked flask, 41g (0.25mol) of 4-ethylbenzohydroxamide, 60ml of methanol, 500ml of cyclohexane, 54.3g (0.3mol) of tetramethylammonium hydroxide pentahydrate and 0.6g of nickel oxide-supported activated carbon (catalyst A1) were charged. Stirring and controlling the temperature to 45 ℃ under the protection of nitrogen, slowly dropping 36.75g (0.375mol) of 2-propyl acrolein, carrying out heat preservation reaction for 8h after dropping, controlling in TLC, ensuring that the raw material is qualified, separating liquid, washing an organic layer to be neutral by 100ml of water, passing 10g of silica gel and 5g of alumina through a column, carrying out reduced pressure concentration on a filtrate to obtain 56.1g of 2- (4-ethyl phenyl) -5-propyl-pyrimidine crude product, crystallizing the crude product for three times by 100ml of methanol to be qualified, airing, 51.4g (56.5 g of theory), ensuring the yield to be 91 wt% and detecting the purity (99.9%) by a gas phase. The gas phase spectrum is shown in FIG. 3, and the mass spectrum is shown in FIG. 4.
Examples 2 to 3
The differences from example 2-1 are: the catalyst was a 2.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 75% by weight, the purity being determined in the gas phase (99.9%).
Examples 2 to 4
The differences from example 2-1 are: the catalyst was a 3.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 68% by weight, the purity being determined in the gas phase (99.9%).
Examples 2 to 5
The differences from example 2-1 are: the catalyst was a 4.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 85.6% by weight, the purity (99.9%) being determined in the gas phase.
Examples 2 to 6
The differences from example 2-1 are: the catalyst was a 5.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 93.3% by weight, the purity (99.9%) being determined in the gas phase.
Examples 2 to 7
The differences from example 2-1 are: the catalyst was a 6.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 80.1% by weight, the purity (99.9%) being determined in the gas phase.
Examples 2 to 8
The differences from example 2-1 are: the molar ratio of the 3, 4-difluorobenzohydroxamamine to the 2-propylacrolein to the sodium methoxide to the catalyst is 1:1.05:1:0.01.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 82.4% by weight, the purity (99.9%) being determined in the gas phase.
Examples 2 to 9
The differences from example 2-1 are: the molar ratio of the 3, 4-difluorobenzohydroxamamine, the 2-propylacrolein, the sodium methoxide and the catalyst is 1:1.5:1.5: 0.05.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 94% by weight, the purity being determined in the gas phase (99.9%).
Examples 2 to 10
The differences from example 2-1 are: the molar ratio of the 3, 4-difluorobenzohydroxamamine to the 2-propylacrolein to the sodium methoxide to the catalyst is 1:1:0.9: 0.005.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 72.3% by weight, the purity (99.9%) being determined in the gas phase.
Examples 2 to 11
The differences from example 2-1 are: the temperature of the cyclization reaction was 40 ℃.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 85.6% by weight, the purity (99.9%) being determined in the gas phase.
Examples 2 to 12
The differences from examples 2 to 13 are: the temperature of the cyclization reaction is 90 ℃.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 71.3% by weight, the purity (99.9%) being determined in the gas phase.
Examples 2 to 13
The differences from examples 2 to 13 are: the temperature of the cyclization reaction was 30 ℃.
The yield of 2- (3, 4-difluorophenyl) -5-propyl-pyrimidine was 65.0% by weight, the purity (95.11%) being determined in the gas phase.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the synthesis method is favorable for greatly improving the utilization rate of raw materials, simplifying the process flow and simultaneously improving the yield and purity of the pyrimidine derivatives and the environmental protection of the process.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The nickel catalyst is characterized by comprising an active ingredient and a carrier, wherein the active ingredient comprises nickel oxide, and the specific surface area of the carrier is 2300-2800 m2/g。
2. The nickel catalyst according to claim 1, wherein the loading of the nickel oxide in the nickel catalyst is 6 to 8 wt%.
3. The nickel catalyst according to claim 1 or 2, characterized in that the support is selected from one or more of the group consisting of activated carbon, diatomaceous earth and alumina.
4. A method for preparing the nickel catalyst according to any one of claims 1 to 3, comprising:
in the presence of a carrier, carrying out a precipitation reaction on a soluble nickel salt and an alkaline aqueous solution so as to load a product of the precipitation reaction in the carrier to obtain a precursor;
and roasting the precursor to obtain the nickel catalyst.
5. The method for preparing a nickel catalyst according to claim 4, wherein the temperature in the calcination step is 380 to 430 ℃.
6. The method for preparing a nickel catalyst according to claim 4 or 5, wherein the soluble nickel salt is one or more selected from the group consisting of nickel chloride, nickel bromide and nickel sulfate; the alkali in the alkaline aqueous solution is selected from one or more of the group consisting of sodium carbonate, potassium carbonate and lithium carbonate;
preferably, the ratio of moles of the soluble nickel salt to moles of base in the aqueous alkaline solution is 1: (1.1-1.5).
7. A method for synthesizing a pyrimidine derivative, which comprises the following steps:
in the presence of the nickel-containing catalyst, the first alkaline reagent, the inert atmosphere and the first organic solvent, 2-alkylacrolein and amidoxime amine are subjected to a cyclization reaction to obtain the pyrimidine derivative, wherein the synthetic route is as follows:
wherein R is1Is selected from C1~C15Fat of (C)1~C30Aryl and C1~C30Cycloalkyl, or a substituent formed by substitution of the above groups by oxygen atoms, halogen or nitrogen atoms, R2Is C1~C15Or substituted by an oxygen atom, a halogen atom or a nitrogen atom to form a substituent, the first organic solvent comprises a first component and a second component, the first component is an alcohol solvent, and the second component is one or more of the group consisting of cyclohexane, petroleum ether, n-hexane and n-heptane.
8. The method for synthesizing pyrimidine derivatives according to claim 7, wherein the molar ratio of the amidoxime, the 2-alkylacrolein, the nickel-containing catalyst and the first alkaline agent is 1 (1.05-1.5): (0.01-0.05): 1.0-1.5.
9. A synthesis method of pyrimidine derivatives according to claim 7 or 8, wherein the temperature of the ring closing reaction is 40-90 ℃.
10. A method of synthesizing pyrimidine derivatives according to claim 9, wherein the first basic reagent is selected from the group consisting of sodium methoxide, sodium carbonate, potassium carbonate, sodium hydroxide, and tetramethylammonium hydroxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011541701.8A CN112675850A (en) | 2020-12-23 | 2020-12-23 | Nickel catalyst, preparation method thereof and synthesis method of pyrimidine derivatives |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011541701.8A CN112675850A (en) | 2020-12-23 | 2020-12-23 | Nickel catalyst, preparation method thereof and synthesis method of pyrimidine derivatives |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112675850A true CN112675850A (en) | 2021-04-20 |
Family
ID=75451223
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011541701.8A Pending CN112675850A (en) | 2020-12-23 | 2020-12-23 | Nickel catalyst, preparation method thereof and synthesis method of pyrimidine derivatives |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112675850A (en) |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5959669A (en) * | 1982-09-02 | 1984-04-05 | アイシ−アイ・オ−ストラリア・リミテイド | Cyclohexan-1,3-dione derivative, manufacture and herbicide composition |
US20020077250A1 (en) * | 2000-09-26 | 2002-06-20 | Markus Eckert | Process for preparing aryl compounds |
US6413676B1 (en) * | 1999-06-28 | 2002-07-02 | Lithium Power Technologies, Inc. | Lithium ion polymer electrolytes |
CN1401428A (en) * | 2002-07-13 | 2003-03-12 | 苏州大学 | Carried chromium-free high-temp. transformation catalyst and preparing process thereof |
TWI242045B (en) * | 2001-03-26 | 2005-10-21 | Cheng Technology Corp | Image-directed chemical synthesis |
CN101041139A (en) * | 2007-04-30 | 2007-09-26 | 京福马(北京)石油化工高新技术有限公司 | Catalyzer for regenerating the waste lubricant oil by hydrogenation and the preparing method |
CN102186864A (en) * | 2008-11-07 | 2011-09-14 | 科莱恩金融(Bvi)有限公司 | Method for producing dialkylphosphinic acids and esters and salts thereof by means of acrylic acid derivatives and use thereof |
US20120041009A1 (en) * | 2009-05-18 | 2012-02-16 | Sumitomo Chemical Company, Limited | Pyrimidine compound and its use in pest control |
CN103145168A (en) * | 2013-02-28 | 2013-06-12 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Particle-size-controllable nano and sub-micron CeO2 preparation method |
CN106035343A (en) * | 2010-07-20 | 2016-10-26 | 韦斯塔隆公司 | Insecticidal triazines and pyrimidines |
CN106380444A (en) * | 2016-08-17 | 2017-02-08 | 南京红太阳生物化学有限责任公司 | A method of preparing 2,2'-bipyridine |
CN106536481A (en) * | 2014-06-19 | 2017-03-22 | 梅里亚股份有限公司 | Parasiticidal compositions comprising indole derivatives, methods and uses thereof |
CN107081154A (en) * | 2017-04-21 | 2017-08-22 | 南昌大学 | One kind is used for CH4The preparation method of complete oxidation high-ratio surface NiO catalyst |
CN107376921A (en) * | 2017-09-01 | 2017-11-24 | 中国科学院上海硅酸盐研究所苏州研究院 | A kind of Sewage advanced treatment graphene porous oxidation nickel composite catalyst and its preparation method and application |
CN109678648A (en) * | 2018-12-29 | 2019-04-26 | 江苏广域化学有限公司 | A method of thick cyclics of the synthesis containing biphenyl structural |
CN111689494A (en) * | 2020-06-23 | 2020-09-22 | 新疆大学 | Non-corrosive catalyst and method for preparing activated carbon by catalytic activation |
-
2020
- 2020-12-23 CN CN202011541701.8A patent/CN112675850A/en active Pending
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5959669A (en) * | 1982-09-02 | 1984-04-05 | アイシ−アイ・オ−ストラリア・リミテイド | Cyclohexan-1,3-dione derivative, manufacture and herbicide composition |
US6413676B1 (en) * | 1999-06-28 | 2002-07-02 | Lithium Power Technologies, Inc. | Lithium ion polymer electrolytes |
US20020077250A1 (en) * | 2000-09-26 | 2002-06-20 | Markus Eckert | Process for preparing aryl compounds |
TWI242045B (en) * | 2001-03-26 | 2005-10-21 | Cheng Technology Corp | Image-directed chemical synthesis |
CN1401428A (en) * | 2002-07-13 | 2003-03-12 | 苏州大学 | Carried chromium-free high-temp. transformation catalyst and preparing process thereof |
CN101041139A (en) * | 2007-04-30 | 2007-09-26 | 京福马(北京)石油化工高新技术有限公司 | Catalyzer for regenerating the waste lubricant oil by hydrogenation and the preparing method |
CN102186864A (en) * | 2008-11-07 | 2011-09-14 | 科莱恩金融(Bvi)有限公司 | Method for producing dialkylphosphinic acids and esters and salts thereof by means of acrylic acid derivatives and use thereof |
US20120041009A1 (en) * | 2009-05-18 | 2012-02-16 | Sumitomo Chemical Company, Limited | Pyrimidine compound and its use in pest control |
CN106035343A (en) * | 2010-07-20 | 2016-10-26 | 韦斯塔隆公司 | Insecticidal triazines and pyrimidines |
CN103145168A (en) * | 2013-02-28 | 2013-06-12 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Particle-size-controllable nano and sub-micron CeO2 preparation method |
CN106536481A (en) * | 2014-06-19 | 2017-03-22 | 梅里亚股份有限公司 | Parasiticidal compositions comprising indole derivatives, methods and uses thereof |
CN106380444A (en) * | 2016-08-17 | 2017-02-08 | 南京红太阳生物化学有限责任公司 | A method of preparing 2,2'-bipyridine |
CN107081154A (en) * | 2017-04-21 | 2017-08-22 | 南昌大学 | One kind is used for CH4The preparation method of complete oxidation high-ratio surface NiO catalyst |
CN107376921A (en) * | 2017-09-01 | 2017-11-24 | 中国科学院上海硅酸盐研究所苏州研究院 | A kind of Sewage advanced treatment graphene porous oxidation nickel composite catalyst and its preparation method and application |
CN109678648A (en) * | 2018-12-29 | 2019-04-26 | 江苏广域化学有限公司 | A method of thick cyclics of the synthesis containing biphenyl structural |
CN111689494A (en) * | 2020-06-23 | 2020-09-22 | 新疆大学 | Non-corrosive catalyst and method for preparing activated carbon by catalytic activation |
Non-Patent Citations (18)
Title |
---|
JIANFEI DING ET AL.: "Catalytic dehydrogenation of isobutane in the presence of carbon dioxide over nickel supported on active carbon", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
JIANFEI DING ET AL.: "Catalytic dehydrogenation of isobutane in the presence of carbon dioxide over nickel supported on active carbon", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 315, 2 October 2009 (2009-10-02), pages 221 - 225, XP026765057, DOI: 10.1016/j.molcata.2009.09.015 * |
JUN TAO ET AL.: "Catalytic Cracking of Biomass High-Temperature Pyrolysis Tar Using NiO/AC Catalysts", 《INTERNATIONAL JOURNAL OF GREEN ENERGY》 * |
JUN TAO ET AL.: "Catalytic Cracking of Biomass High-Temperature Pyrolysis Tar Using NiO/AC Catalysts", 《INTERNATIONAL JOURNAL OF GREEN ENERGY》, vol. 12, 20 October 2014 (2014-10-20), pages 773 * |
PING LU ET AL.: "Syntheses, structures, catalytic and antitumor activities of a series of pyrimidine derivatives coordination complexes", 《SYNTHETIC METALS》 * |
PING LU ET AL.: "Syntheses, structures, catalytic and antitumor activities of a series of pyrimidine derivatives coordination complexes", 《SYNTHETIC METALS》, vol. 203, 31 May 2015 (2015-05-31), pages 164 - 173, XP029582861, DOI: 10.1016/j.synthmet.2015.02.024 * |
XUE-QIANG CHU ET AL.: "Iron Catalysis for Modular Pyrimidine Synthesis through β‑Ammoniation/Cyclization of Saturated Carbonyl Compounds with Amidines", 《J. ORG. CHEM.》 * |
XUE-QIANG CHU ET AL.: "Iron Catalysis for Modular Pyrimidine Synthesis through β‑Ammoniation/Cyclization of Saturated Carbonyl Compounds with Amidines", 《J. ORG. CHEM.》, vol. 82, 29 December 2016 (2016-12-29), pages 1145 - 1154 * |
刘雪景: "活性炭负载镍催化剂的制备及催化甲苯水蒸气重整研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 2, pages 014 - 1419 * |
周五青: "生物质炭负载镍催化裂解甲苯的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 3, pages 016 - 1021 * |
唐嘉等: "活性炭负载过渡金属催化剂的制备及催化性能研究", 《黑龙江大学自然科学学报》, vol. 33, no. 1, pages 82 - 88 * |
温俊峰等: "Ni-Cu/AC催化剂的制备及其催化氧化甲醇羰基化反应性能研究", 《科学技术与工程》, no. 34, pages 9400 - 9402 * |
王益平等: "NiO/AC催化臭氧氧化去除水中的苯酚", 《环境工程学报》 * |
王益平等: "NiO/AC催化臭氧氧化去除水中的苯酚", 《环境工程学报》, vol. 4, no. 11, 30 November 2010 (2010-11-30), pages 2441 - 2445 * |
许飞等: "NiO/AC催化剂上异丁烷与CO2耦合脱氢反应研究", 《化工时刊》 * |
许飞等: "NiO/AC催化剂上异丁烷与CO2耦合脱氢反应研究", 《化工时刊》, vol. 34, no. 7, 31 July 2020 (2020-07-31), pages 1 - 4 * |
郭家秀等: "Ni物种形态对Ni/AC催化剂低温脱硫性能的影响", 《催化学报》 * |
郭家秀等: "Ni物种形态对Ni/AC催化剂低温脱硫性能的影响", 《催化学报》, vol. 31, no. 3, 30 March 2010 (2010-03-30), pages 278 - 282 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109803955B (en) | Process for the preparation of 4-ammonium-2, 2,6, 6-tetraalkylpiperidinium salts | |
Hausdorf et al. | Proton and water activity-controlled structure formation in zinc carboxylate-based metal organic frameworks | |
Zhu et al. | Zeolitic metal azolate frameworks (MAFs) from ZnO/Zn (OH) 2 and monoalkyl-substituted imidazoles and 1, 2, 4-triazoles: Efficient syntheses and properties | |
CN105153058A (en) | Synthetic method of benzotriazoles compound | |
US20160024120A1 (en) | Azolium Metal-Organic Frameworks | |
CN102381976B (en) | Method for preparing 1, 4-cyclohexane dioctyl phthalate dimethyl | |
CN109678648B (en) | Method for synthesizing fused ring compound containing biphenyl structure | |
CN112675850A (en) | Nickel catalyst, preparation method thereof and synthesis method of pyrimidine derivatives | |
CN113578275A (en) | For NOxManganese-cobalt binary metal-based MOF adsorbent for gas removal and preparation method thereof | |
CN102380374A (en) | Preparation method of palladium group hydrogenation catalyst | |
KR101091875B1 (en) | A purification method of porous metal-organic framework materials | |
JP2014012251A (en) | Gas separation material containing metal complex of oxocarbonic acid, and separation method of hydrocarbon gas | |
CN108409647A (en) | A kind of Ah pa replaces the preparation method of Buddhist nun | |
CN113292581B (en) | Novel coordination circular polarization luminescent crystalline compound and preparation method and application thereof | |
CN112159388B (en) | Preparation method of vinyl sulfate derivative | |
CN110156641B (en) | Synthesis method of substituted guanidine | |
US10011603B2 (en) | Process for preparing a carbapenem antibiotic | |
CN111137903B (en) | ECNU-25 molecular sieve and preparation method and application thereof | |
JP5152895B2 (en) | Method for producing cyclic alkyleneimine | |
CN111517337A (en) | ECNU-24 molecular sieve and preparation method and application thereof | |
CN101088999A (en) | Process of synthesizing 3-amino quinine dihydrochloride | |
CN104549323A (en) | Method for synthesizing 1,2-dimethyl imidazole and supported catalyst for method | |
CN111116483B (en) | 2-imidazolyl imidazole compound and preparation method thereof | |
CN103204845B (en) | Imidazolyl ionic liquid, and synthesizing method and application thereof | |
CN115919817B (en) | Gem diselenide compound and its synthesis method and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210420 |
|
WD01 | Invention patent application deemed withdrawn after publication |